US3676442A - Synthesis of pyrazines - Google Patents

Synthesis of pyrazines Download PDF

Info

Publication number: US3676442A
Authority: US; United States
Prior art keywords: process according; formate; acetylene compound; acid; acetylene
Prior art date: 1968-11-22
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Expired - Lifetime

Application number

US878941A

Other languages

English (en)

Inventor

Albert Bonzom

Bernard Tramier

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Societe Nationale des Petroles dAquitaine SA

Original Assignee

Societe Nationale des Petroles dAquitaine SA

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1968-11-22

Filing date

1969-11-21

Publication date

1972-07-11

1969-11-21 Application filed by Societe Nationale des Petroles dAquitaine SA filed Critical Societe Nationale des Petroles dAquitaine SA

1972-07-11 Application granted granted Critical

1972-07-11 Publication of US3676442A publication Critical patent/US3676442A/en

1989-07-11 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

150000003216 pyrazines Chemical class 0.000 title abstract description 15
230000015572 biosynthetic process Effects 0.000 title description 8
238000003786 synthesis reaction Methods 0.000 title description 4
-1 acetylene compound Chemical class 0.000 claims abstract description 42
BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 37
HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 26
235000019253 formic acid Nutrition 0.000 claims abstract description 22
OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 15
BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims abstract description 14
239000002253 acid Substances 0.000 claims abstract description 12
238000006243 chemical reaction Methods 0.000 claims abstract description 12
238000000034 method Methods 0.000 claims description 31
229940013688 formic acid Drugs 0.000 claims description 14
150000003863 ammonium salts Chemical class 0.000 claims description 10
125000004432 carbon atom Chemical group C* 0.000 claims description 9
239000012429 reaction media Substances 0.000 claims description 9
239000002904 solvent Substances 0.000 claims description 7
ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 6
XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
150000003839 salts Chemical class 0.000 claims description 5
UIGLAZDLBZDVBL-UHFFFAOYSA-N 1-phenylprop-2-yn-1-ol Chemical compound C#CC(O)C1=CC=CC=C1 UIGLAZDLBZDVBL-UHFFFAOYSA-N 0.000 claims description 4
QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
239000004202 carbamide Substances 0.000 claims description 4
CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
229910019142 PO4 Inorganic materials 0.000 claims description 3
KDIDLLIMHZHOHO-UHFFFAOYSA-N prop-2-ynyl formate Chemical compound O=COCC#C KDIDLLIMHZHOHO-UHFFFAOYSA-N 0.000 claims description 3
229940095064 tartrate Drugs 0.000 claims description 3
AVMNFQHJOOYCAP-UHFFFAOYSA-N acetic acid;propanoic acid Chemical compound CC(O)=O.CCC(O)=O AVMNFQHJOOYCAP-UHFFFAOYSA-N 0.000 claims description 2
239000003054 catalyst Substances 0.000 claims description 2
239000000463 material Substances 0.000 claims description 2
NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
239000010452 phosphate Substances 0.000 claims description 2
125000005514 but-1-yn-3-yl group Chemical group 0.000 claims 2
GKPOMITUDGXOSB-UHFFFAOYSA-N but-3-yn-2-ol Chemical compound CC(O)C#C GKPOMITUDGXOSB-UHFFFAOYSA-N 0.000 claims 1
239000004215 Carbon black (E152) Substances 0.000 abstract description 4
229930195733 hydrocarbon Natural products 0.000 abstract description 4
125000004430 oxygen atom Chemical group O* 0.000 abstract description 4
150000003868 ammonium compounds Chemical class 0.000 abstract description 2
125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 14
QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 7
238000002360 preparation method Methods 0.000 description 7
HJFZAYHYIWGLNL-UHFFFAOYSA-N 2,6-Dimethylpyrazine Chemical compound CC1=CN=CC(C)=N1 HJFZAYHYIWGLNL-UHFFFAOYSA-N 0.000 description 6
FINHMKGKINIASC-UHFFFAOYSA-N Tetramethylpyrazine Chemical compound CC1=NC(C)=C(C)N=C1C FINHMKGKINIASC-UHFFFAOYSA-N 0.000 description 6
150000001408 amides Chemical class 0.000 description 5
150000002148 esters Chemical class 0.000 description 5
125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
239000001934 2,5-dimethylpyrazine Substances 0.000 description 4
QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
ZRLDBDZSLLGDOX-UHFFFAOYSA-N Trimethyloxazole Chemical compound CC1=NC(C)=C(C)O1 ZRLDBDZSLLGDOX-UHFFFAOYSA-N 0.000 description 4
235000013877 carbamide Nutrition 0.000 description 4
150000007513 acids Chemical class 0.000 description 3
125000000217 alkyl group Chemical group 0.000 description 3
238000009833 condensation Methods 0.000 description 3
230000005494 condensation Effects 0.000 description 3
150000002430 hydrocarbons Chemical group 0.000 description 3
125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
229920000137 polyphosphoric acid Polymers 0.000 description 3
239000007858 starting material Substances 0.000 description 3
LCZUOKDVTBMCMX-UHFFFAOYSA-N 2,5-Dimethylpyrazine Chemical compound CC1=CN=C(C)C=N1 LCZUOKDVTBMCMX-UHFFFAOYSA-N 0.000 description 2
YVORRVFKHZLJGZ-UHFFFAOYSA-N 4,5-Dimethyloxazole Chemical compound CC=1N=COC=1C YVORRVFKHZLJGZ-UHFFFAOYSA-N 0.000 description 2
PUMREIFKTMLCAF-UHFFFAOYSA-N 4-methyl-1,3-oxazole Chemical compound CC1=COC=N1 PUMREIFKTMLCAF-UHFFFAOYSA-N 0.000 description 2
HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
150000001298 alcohols Chemical class 0.000 description 2
125000001931 aliphatic group Chemical group 0.000 description 2
229910021529 ammonia Inorganic materials 0.000 description 2
VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical group [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 2
125000003118 aryl group Chemical group 0.000 description 2
229910052799 carbon Inorganic materials 0.000 description 2
150000001875 compounds Chemical class 0.000 description 2
229910052739 hydrogen Inorganic materials 0.000 description 2
238000004519 manufacturing process Methods 0.000 description 2
239000000203 mixture Substances 0.000 description 2
150000002916 oxazoles Chemical class 0.000 description 2
235000021317 phosphate Nutrition 0.000 description 2
238000006116 polymerization reaction Methods 0.000 description 2
239000000376 reactant Substances 0.000 description 2
238000010992 reflux Methods 0.000 description 2
239000000126 substance Substances 0.000 description 2
DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 1
MUENINFVGCDNTE-UHFFFAOYSA-N 1-(2-chlorophenyl)prop-2-yn-1-ol Chemical compound C#CC(O)C1=CC=CC=C1Cl MUENINFVGCDNTE-UHFFFAOYSA-N 0.000 description 1
OCGGBKUCKYBJSC-UHFFFAOYSA-N 1-phenylbut-3-yn-2-ol Chemical compound C#CC(O)CC1=CC=CC=C1 OCGGBKUCKYBJSC-UHFFFAOYSA-N 0.000 description 1
LQIGIQZSHAYEKN-UHFFFAOYSA-N 2,6-Diethyl-3,5-dimethylpyrazine Chemical compound CCC1=NC(CC)=C(C)N=C1C LQIGIQZSHAYEKN-UHFFFAOYSA-N 0.000 description 1
BIRAXIXWDGHXLO-UHFFFAOYSA-N 2,6-dimethyl-3,5-diphenylpyrazine Chemical compound CC1=NC(C)=C(C=2C=CC=CC=2)N=C1C1=CC=CC=C1 BIRAXIXWDGHXLO-UHFFFAOYSA-N 0.000 description 1
241000193830 Bacillus <bacterium> Species 0.000 description 1
FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
239000004952 Polyamide Substances 0.000 description 1
KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
150000001242 acetic acid derivatives Chemical class 0.000 description 1
125000002877 alkyl aryl group Chemical group 0.000 description 1
239000002269 analeptic agent Substances 0.000 description 1
230000003555 analeptic effect Effects 0.000 description 1
150000001450 anions Chemical class 0.000 description 1
125000003710 aryl alkyl group Chemical group 0.000 description 1
150000005840 aryl radicals Chemical class 0.000 description 1
125000004429 atom Chemical group 0.000 description 1
229940077388 benzenesulfonate Drugs 0.000 description 1
SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
150000001558 benzoic acid derivatives Chemical class 0.000 description 1
238000009835 boiling Methods 0.000 description 1
KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical class CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 1
150000004648 butanoic acid derivatives Chemical class 0.000 description 1
239000006227 byproduct Substances 0.000 description 1
150000001721 carbon Chemical group 0.000 description 1
150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
150000001733 carboxylic acid esters Chemical class 0.000 description 1
125000000068 chlorophenyl group Chemical group 0.000 description 1
230000000694 effects Effects 0.000 description 1
239000000839 emulsion Substances 0.000 description 1
238000000605 extraction Methods 0.000 description 1
AHHYEKPJZYDDFK-UHFFFAOYSA-N formic acid;phosphoric acid Chemical compound OC=O.OP(O)(O)=O AHHYEKPJZYDDFK-UHFFFAOYSA-N 0.000 description 1
229910052736 halogen Inorganic materials 0.000 description 1
150000002367 halogens Chemical class 0.000 description 1
SRSOGIWDNSFTEG-UHFFFAOYSA-N hex-4-en-1-yn-3-ol Chemical compound CC=CC(O)C#C SRSOGIWDNSFTEG-UHFFFAOYSA-N 0.000 description 1
GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
239000001257 hydrogen Substances 0.000 description 1
239000003112 inhibitor Substances 0.000 description 1
229910052500 inorganic mineral Chemical class 0.000 description 1
150000002576 ketones Chemical class 0.000 description 1
229910052943 magnesium sulfate Inorganic materials 0.000 description 1
235000019341 magnesium sulphate Nutrition 0.000 description 1
238000002844 melting Methods 0.000 description 1
230000008018 melting Effects 0.000 description 1
150000002730 mercury Chemical class 0.000 description 1
229910052751 metal Inorganic materials 0.000 description 1
239000002184 metal Substances 0.000 description 1
239000011707 mineral Chemical class 0.000 description 1
235000010755 mineral Nutrition 0.000 description 1
238000006386 neutralization reaction Methods 0.000 description 1
238000011017 operating method Methods 0.000 description 1
150000007524 organic acids Chemical class 0.000 description 1
LBSKEFWQPNVWTP-UHFFFAOYSA-N pent-1-yn-3-ol Chemical compound CCC(O)C#C LBSKEFWQPNVWTP-UHFFFAOYSA-N 0.000 description 1
239000000825 pharmaceutical preparation Substances 0.000 description 1
229940127557 pharmaceutical product Drugs 0.000 description 1
239000012071 phase Substances 0.000 description 1
125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
150000003014 phosphoric acid esters Chemical class 0.000 description 1
150000004885 piperazines Chemical class 0.000 description 1
229920002647 polyamide Polymers 0.000 description 1
229920000728 polyester Polymers 0.000 description 1
229940072033 potash Drugs 0.000 description 1
BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
235000015320 potassium carbonate Nutrition 0.000 description 1
239000000047 product Substances 0.000 description 1
NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical class NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
229910021653 sulphate ion Inorganic materials 0.000 description 1
150000003672 ureas Chemical class 0.000 description 1
239000012808 vapor phase Substances 0.000 description 1
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

Definitions

the invention relates to a new process for the synthesis of substituted pyrazines, and more particularly of those of which the carbon atoms in the 2 and 6-positions or 2, 3, 5 and 6-positions carry hydrocarbon substituents.
the present invention provides a new process which permits the aforementioned derivatives to be obtained in a more practical manner with good yields. It is based on the use of certain acetylene compounds, which are becoming increasingly accessible at the present time.
the new process consists in causing the reaction, in acid medium, of an ammoniacal derivative with an acetylene compounds of which the carbon atom in the a-position of the triple bond carries an oxygen atom connecting it to another grouping or atom.
One very important characteristic of the invention consists in the presence of formic groups in the reaction medium, thus ensuring a good yield of substituted pyrazine.
Ammoniacal derivative is any compound containing NH groups, particularly CONl-l or NH groups, whether free or combined, such as amides, ammonium salts, ureas, etc.
the preferred ammoniacal derivative is ammonium formate; formamide is also suitable, but it is desirable to use it concurrently with formic acid.
acetylene compounds which can be used according to the invention can be represented by the general formula:
R and R' are hydrogen atoms or hydrocarbon radicals, particularly alkyls, cycloaklyls, aryls, aralkyls, alkaryls, which are possibly substituted with non-labile groups in acid medium, as for example halogens; the process is especially suitable in those cases where R and/or R are hydrogens or linear or branched alkyls from C to C
The, symbol A represents a group such as --OH, OOCR", -SO R' etc., R" being any aliphatic or aryl radical capable of forming the residue of an organic acid; in general terms, A is a group having an oxygen atom bonded to the carbon in the a-position with respect to the triple bond.
acetylene compounds which can be most usually employed are the a-acetylene alcohols (A being OH) and their esters (A being --OOCR”)
A OH
A esters
esters are provided by the carboxylic acid esters, more especially aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic carboxylic acid esters, or mineral acids, of the aforementioned acetylene alcohols. It is thus possible, inter alia, to use the acetates, propionates, butyrates, benzoates, benzene sulphonates, sulphates, phosphates, etc. of prop-l-yn-B-yl, but-l-yn-3-yl, pent-l-yn-3- yl, ethynyl phenyl or any other acetylene radical in the 1,3- position.
the preferred method of procedure, when esters are used consists in taking as starting material the formate of the selected acetylene radical.
the acid medium necessary for the reaction represents at the same time the solvent of the initial materials, it is possible .to use various acids, for example, acetic acid and especially formic acid, but particularly interesting results are obtained with anhydrous polyphosphoric acid.
Another solvent is, for example, hexamethyl phosphotriamide.
the concentrationof the reactants in their acid solution is generally of the order of 10 to 70 percent and usually about 30 to 60 percent by weight.
the proportion of ammoniacal derivative is stoichiometric or in excess with respect to the acetylene compound.
substituted pyrazines according to the invention is catalyzed by metal salts, particularly mercury salts. It is possible to employ a salt with a monovalent or polyvalent anion, for example, chloride, bromide, sulphate, phosphate formate, acetate, propionate, oxalate, tartrate, etc., but this list is not in any way limiting.
metal salts particularly mercury salts.
a salt with a monovalent or polyvalent anion for example, chloride, bromide, sulphate, phosphate formate, acetate, propionate, oxalate, tartrate, etc., but this list is not in any way limiting.
the reaction takes place at a temperature which can vary, for example, between 50 and 200 C and usually from to C.
the 2,6-dimethyl pyrazine was extracted with ether from the reaction medium.
the latter was first of all neutralized with concentrated potash and subjected to continuous extraction with ether. After 6 hours, the ethereal phase was dried over anhydrous magnesium sulphate and distilled. The fraction containing the 4-methyl oxazole passes over between 78 and 82 C; all that which passes over above 90 C is eliminated, and the 2,6-dimethyl pyrazine is obtained, boiling at 150-l52 C.
Example 22 Operating as in Example 3, but starting with phenyl ethynyl carbinol, the 3,5-diphenyl-2,6-dimethyl pyrazine was obtained with a yield of 32 percent calculated on the carbinol.
a process for the preparation of hydrocarbon substituted pyrazine comprising reacting a compound selected from the group consisting of formarnide, ammonium salts and urea in an acid solvent selected from the group consisting of formic acid, acetic acid, polyphosphoric acid and hexamethylphosphotriarnide, with an acetylene compound of the formula:
R and R are independently selected from the group consisting of hydrogen, alkyl having from one to 18 carbon atoms, phenyl and chlorophenyl, and A is selected from the group consisting of OH and the formate, acetate, propionate, butyrate, benzoate, benzene sulfonate, sulfate and phosphate esters thereof, at a temperature from about 50 to about 200 C.
reaction medium contains a mercuric salt selected from the group consisting of chloride, bromide, sulfate, phosphate, formate, acetate propionate, oxalate and tartrate, as a catalyst.
reaction medium contains at least 1 mole of formic acid per mole of acetylene compound.
acetylene compound is selected from the group consisting of propargyl alcohol, propargyl formate, but-l-yn-S-ol, but-l-yn-3-yl formate, but-l-yn-S-yl acetate, pent-l-yl-3-ol and phenyl ethynyl carbinol.

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Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Nitrogen Condensed Heterocyclic Rings (AREA)
Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Catalysts (AREA)

US878941A 1968-11-22 1969-11-21 Synthesis of pyrazines Expired - Lifetime US3676442A (en)

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
FR174829		1968-11-22

Publications (1)

Publication Number	Publication Date
US3676442A true US3676442A (en)	1972-07-11

Family

ID=8657242

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
US878941A Expired - Lifetime US3676442A (en)	1968-11-22	1969-11-21	Synthesis of pyrazines

Country Status (8)

Country	Link
US (1)	US3676442A (fr)
BE (1)	BE742051A (fr)
CH (1)	CH519506A (fr)
DE (1)	DE1958619C3 (fr)
FR (1)	FR1593328A (fr)
GB (1)	GB1292852A (fr)
LU (1)	LU59849A1 (fr)
NL (1)	NL161143C (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US6225471B1 (en) *	1991-03-26	2001-05-01	Nestec S.A.	Preparation of pyrazines

Citations (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US3453278A (en) *	1967-04-06	1969-07-01	Gulf Research Development Co	Preparation of hydrocarbon-substituted pyrazines and piperazines from alpha-nitro-ketones

1968
- 1968-11-22 FR FR174829A patent/FR1593328A/fr not_active Expired
1969
- 1969-11-18 CH CH1710869A patent/CH519506A/fr not_active IP Right Cessation
- 1969-11-19 GB GB56598/69A patent/GB1292852A/en not_active Expired
- 1969-11-20 LU LU59849D patent/LU59849A1/xx unknown
- 1969-11-21 NL NL6917544.A patent/NL161143C/xx not_active IP Right Cessation
- 1969-11-21 BE BE742051D patent/BE742051A/xx unknown
- 1969-11-21 DE DE1958619A patent/DE1958619C3/de not_active Expired
- 1969-11-21 US US878941A patent/US3676442A/en not_active Expired - Lifetime

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US3453278A (en) *	1967-04-06	1969-07-01	Gulf Research Development Co	Preparation of hydrocarbon-substituted pyrazines and piperazines from alpha-nitro-ketones

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US6225471B1 (en) *	1991-03-26	2001-05-01	Nestec S.A.	Preparation of pyrazines

Also Published As

Publication number	Publication date
NL161143C (nl)	1980-01-15
NL161143B (nl)	1979-08-15
NL6917544A (fr)	1970-05-26
DE1958619B2 (de)	1978-06-29
GB1292852A (en)	1972-10-18
LU59849A1 (fr)	1970-01-20
DE1958619C3 (de)	1979-03-15
CH519506A (fr)	1972-02-29
BE742051A (fr)	1970-05-21
DE1958619A1 (de)	1970-06-11
FR1593328A (fr)	1970-05-25

Publication	Publication Date	Title
US2449987A (en)	1948-09-28	Preparation of substituted acids from lactones
US2847417A (en)	1958-08-12	Preparation of imidazole compounds
Muraki et al.	1974	Aminoaluminum Hydride as New Reducing Agents. I. Selective Reduction of Carboxylic Acids to Aldehydes
US3676442A (en)	1972-07-11	Synthesis of pyrazines
US2830994A (en)	1958-04-15	Process for manufacture of isonicotinic acid hydrazide from pyridine nitrile
US2517826A (en)	1950-08-08	Beta-(2-benzothienyl)-alpha-amino propionic acid and salts
US5110951A (en)	1992-05-05	Method for producing L-ascorbic acid 2-phosphates
Beecham	1954	The action of ammonia and other bases on γ-methyl and γ-ethyl L-glutamate
JPH0361667B2 (fr)	1991-09-20
US3067199A (en)	1962-12-04	Method for preparing alkyl-substituted piperazines, alkyl-substituted pyrazines, andmixtures thereof
US3492305A (en)	1970-01-27	Non-catalytic preparation of pyridines
US2122813A (en)	1938-07-05	Production of polyhydric alcohols
US3657324A (en)	1972-04-18	Hydrazine derivatives and process therefor
US2473111A (en)	1949-06-14	Process for production of z-amino
US3084168A (en)	1963-04-02	2, 4, 6-tris(2-cyanoalkyl)-trioxanes
US3742014A (en)	1973-06-26	Preparation of benzonitriles
US2455172A (en)	1948-11-30	Production of z-monosubstituted
US3852351A (en)	1974-12-03	Chlorination of acetoacetamides
US3128286A (en)	1964-04-07	Process for preparing analogues
US2717896A (en)	1955-09-13	Certain 4(lower alkyl carboxylic acid acyl) carbethoxypiperazines
US2738363A (en)	1956-03-13	Process for the production of alpha-beta diaminopropionic acid esters
US3084171A (en)	1963-04-02	5-nitro-2-furylamidine and alkyl 5-nitro-2-furylimidate
US2623059A (en)	1952-12-23	Beta-dithiocarbazyl carboxylic acid compounds and their preparation
US3531498A (en)	1970-09-29	Process for the preparation of 2-carboxythiolanes
US2485271A (en)	1949-10-18	Preparation of bis-(2-carboxyalkyl) sulfones

US3676442A - Synthesis of pyrazines - Google Patents

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